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BIOCHEMISTRY

CHAPTER 2
CARBOHYDRATE METABOLISM
LECTURE OUTLINE

• Carbohydrate function and structure

• Carbohydrate metabolism for cellular


respiration

• Aerobic and anaerobic metabolism

• Aerobic fermentation
OBJECTIVES

• To understand the carbohydrate function and structure

• To analyze the carbohydrate metabolism for cellular


respiration

• To differentiate aerobic and anaerobic metabolism to


generate energy
Carbohydrate

• hydrates of carbon
• made up of carbon, hydrogen & oxygen in a
ratio of 1:2:1 → CxH2xOx
• Classification:
Class Monomers
Monosaccharide 1
Disaccharide 2
Trisaccharide 3
Oligosaccharide 2-20
Polysaccharide > 20
Functions of Carbohydrate

• cellular energy storage & source


• structural components
• structural skeleton for DNA & RNA
• role in cellular interactions
• commercials → colourings, paint, papers,
pharmaceuticals
Carbohydrates – polyhydroxyaldehydes or polyhydroxy-
ketones of formula (CH2O)n, or compounds that can be
hydrolyzed to them. (aka sugars or saccharides)
Monosaccharides – carbohydrates that cannot be hydrolyzed
to simpler carbohydrates; eg. Glucose or fructose.
Disaccharides – carbohydrates that can be hydrolyzed into
two monosaccharide units; eg. Sucrose, which is hydrolyzed
into glucose and fructose.
Oligosaccharides – carbohydrates that can be hydrolyzed into
a few monosaccharide units.
Polysaccharides – carbohydrates that are are polymeric
sugars; eg Starch or cellulose.
Aldose – polyhydroxyaldehyde, eg glucose
Ketose – polyhydroxyketone, eg fructose
Triose, tetrose, pentose, hexose, etc. –
carbohydrates that contain three, four, five,
six, etc. carbons per molecule (usually five
or six); eg. Aldohexose, ketopentose, etc.
A. Monosaccharide
Classification is based on:
1. Carbon atom no.
 3C (triose), 4C (tetrose), 5C (pentose), 6C (hexose) etc.

Glyceraldehyde Erythrose Ribose Glucose Fructose


(triose) (tetrose) (pentose) (hexose)
Monosaccharides with various number of carbon atoms
2. Carbonyl functional group
i) polyhydroxy + aldehyde = aldose
ii) polyhydroxy + ketone = ketose
Combination of both
classifications:

Triose which is also an


aldose: aldotriose

Triose which is also a


ketose: ketotriose
Monosaccharides
Aldoses (e.g., glucose) have an Ketoses (e.g., fructose) have
aldehyde group at one end. a keto group, usually at C2.

H O
C CH2OH

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH

D-glucose D-fructose
B. Disaccharides

-2 units of monosaccharides linked by glycosidic bond


- loss of 1 H atom from 1 monosaccharide & 1 OH group
from another monosaccharide by a glycosidase
Examples of disaccharides…

(12)

(14)

(14)
• Glucose + Glucose = maltose
• Fructose + Glucose = Sucrose
• Galactose + Glucose = lactose

• reducing (lactose & maltose) & non-reducing


sugars (sucrose)
C. Oligosaccharides

• Short chain of monosaccharides linked together by


glycosidic bonds

• Oligos linked to protein: glycoproteins


• Oligos linked to lipid: glycolipids

• In glycoproteins, 2 types of linkages:


 N-linked
 O-linked
Did you know…
CH2OH 6CH OH CH2OH CH2OH CH2OH
2
O 5 O H O H O H H O H
H H H H H
H H H H H
OH H 1 4 OH H 1 OH H OH H OH H
O O O O OH
OH 2
3
H OH H OH H OH H OH H OH
amylose

Polysaccharides:
Plants store glucose as amylose or amylopectin, glucose
polymers collectively called starch.
Glucose storage in polymeric form minimizes osmotic
effects.
Amylose is a glucose polymer with (14) linkages.
The major storage polysaccharides are :
• Glycogen (in animals)
• Starch (in plants)
• Dextran (in yeast & bacteria)
The structural polysaccharides are:
• Cellulose – found in plant cell walls
• Chitin – found in animal
Starch
• storage in plants
• polymer of α-glucoses
• 2 types of molecules:
a) amylose → unbranched, α(1→4) bond
b) amylopectin → linear polymer of
α(1→4) with α(1→6) branches every 24-
30 residues
• stored as granules in plastids
• degradation by hydrolysis
CH2OH CH2OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH2OH CH2OH 6 CH2 CH2OH CH2OH


H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH
3 2
H OH H OH H OH H OH H OH

Amylopectin is a glucose polymer with mainly (14) linkages,


but it also has branches formed by (16) linkages.
Glycogen
 polysaccharide storage in animals that has
polymer of α-glucoses
 consist of only amylopectin → every 8-12
residues, more compact than starch
 stored in muscles & liver cells
 degradation by hydrolysis
CH 2OH CH 2OH
H O O
glycogen
H H H
H H
OH H OH H 1
O
OH
O
H OH H OH

CH 2OH CH 2OH 6 CH 2 CH 2OH CH 2OH


H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH 2
3
H OH H OH H OH H OH H OH

Glycogen, the glucose storage polymer in animals, is similar in


structure to amylopectin.
But glycogen has more (16) branches.
The highly branched structure permits rapid glucose release
from glycogen stores, e.g., in muscle during exercise.
Compare…

Glycogen Starch structure


structure
Dextran
• Polymer of glucoses, mainly linked by α(16) bond
• A few branches also occur, typically by α(12) α(13) α(14)
bonds, depending on bacterial/yeast species

Cellulose
• structural polysaccharide  cell wall of plants
• polymer of -glucoses  15000 residues linked by (14)
bond
• degradation by cellulase (not found in humans)

• chitin???  animals polysaccharide (e.g. arthropods)


CH2OH 6CH OH CH2OH CH2OH CH2OH
2
O 5 O O H O H O OH
H H H
H H H H H
OH H 1 O 4 OH H 1 O OH H O OH H O OH H
OH H H H
H 2 H
3
H OH H OH H OH H OH H OH
cellulose

Cellulose, a major constituent of plant cell walls, consists


of long linear chains of glucose with (14) linkages.
Every other glucose is flipped over, due to  linkages.
Carbohydrate Metabolism…

 main sources – starch, glycogen,


disaccharide
 all carbohydrates are converted into
monosaccharides (i.e. glucose)
 glucose will:
 catabolized producing ATP
 stored as glycogen
 converted into fatty acids
Metabolism of Carbohydrates

Carbohydrates are the major energy source for


animals and most microorganisms.

Catabolism of carbohydrates:

Polysaccharides  monosacchrides  ATP

Anabolism of carbohydrates:
ATP ADP
Monosacchrides    polysacchrides
In Cytosol

In Mitochondria
GLYCOLYSIS

 Glycolysis (glyco = sugar; • can proceed under anaerobic


lysis = breaking)‘sweet’ & conditions
‘splitting’
 initial pathway in the
catabolism of • all living organisms used this
carbohydrates process
 occurs in the
cytosol/cytoplasm • divided into two phases –
 simple sugar (i.e. glucose) energy investment phase
split into pyruvate (phase I) & energy generating
phase (phase II)
Aerobic conditions Anaerobic conditions

Krebs/Citric Acid Cycle

Fermentation

Electron Transport Chain

e.g. in e.g. in
muscle yeast

Lactic acid Ethanol


Glycolysis means oxidation of glucose to give pyruvate
(in the presence of oxygen) or lactate (in the absence
of oxygen).
Stages of glycolysis
1. Stage one (the energy requiring stage):
a) One molecule of glucose is converted into two molecules
of glyceroaldhyde-3-phosphate.
b) These steps requires 2 molecules of ATP (energy loss)
2. Stage two (the energy producing stage(:
a) The 2 molecules of glyceroaldehyde-3-phosphate are
converted into pyruvate
b) These steps produce ATP molecules (energy production).
PHASE I: Energy Investment Phase
PHASE II: Energy Generating Phase
Destabilizing the molecule in the previous reaction allows the hexose ring to be split
by aldolase into two triose sugars, dihydroxyacetone phosphate, a ketone,
and glyceraldehyde 3-phosphate, an aldehyde.
• TOTAL ATP PRODUCTION:

– Glycolysis produces 4 ATP's and 2 NADH, but uses


2 ATP's in the process for a net of 2 ATP and
2 NADH
– Glycolysis Step 1 uses 2 ATP molecules
– Glycolysis Step 2 converts 4 ADP molecules
into 4 ATP molecules
– Net ATP production = 2 ATP for every
glucose molecule
Net ATP production = 2 ATP for every glucose molecule
Glycolytic net reaction…

Glucose + 2 ADP + 2 PO42- + 2 NAD+

10 enzymes

2 pyruvate + 2 NADH + 2 H2O + 2 ATP

further metabolized
• Aerobically by converting into acetyl-coa & into citric acid cycle
• Anaerobically by fermentation
2 types:
a) Lactate Fermentation
b) Alcohol Fermentation
Lactate fermentation
• Lactate
• Produced by muscles when the body can’t supply
enough O2.
pyruvate lactate
NADH + H+ NAD+

• Pyruvate is reduced to lactate; NADH loses an H to


become NAD+ (Nicotinamide adenine dinucleotide).
• Lactic Acid Fermentation

o produced by the muscles when O2 is in short


supply, also occurs in some bacteria and some
fungi

– Muscle fatigue
• When your muscle cells require more energy
than can be produced
• Lack of oxygen
• Lactic acid build up = muscle fatigue

• When oxygen is present, lactic acid will be


oxidize / break down
LACTATE FERMENTATION

lactate dehydrogenase
• Alcohol Fermentation

– Occurs in bacteria, plants and most animals


– Can you think of a bacteria that is used for
fermentation???
– Pyruvic Acid is converted into ethanol and
carbon dioxide
– done by yeast and some types of bacteria
– important in bread-making, brewing, and
wine-making
Alcohol fermentation
• Used by anaerobic bacteria to obtain additional energy
from glucose.

pyruvate
pyruvate
decarboxylase

acetaldehyde + CO2
NADH + H+
alcohol
dehydrogenase
NAD+
ethanol
ALCOHOL FERMENTATION

alcohol
dehydrogenase

pyruvate decarboxylase
Aerobic Metabolism
• mechanism whereby energy of the chemical bonds in
food/glucose is stored & used to drive ATP synthesis
• occurs in mitochondria

• processes:
 tricarboxylic acid cycle (TCA cycle)
 e- transport chain (ETC)
• As pyruvate enters the mitochondrion, a
multienzyme complex modifies pyruvate
to acetyl CoA which enters the Krebs
cycle in the matrix.
– A carboxyl group is removed as CO2.
– A pair of electrons is transferred from
the remaining two-carbon fragment
to NAD+ to form NADH.
– The oxidized
fragment, acetate,
combines with
coenzyme A to
form acetyl CoA.
2 NADH's are generated (1 per pyruvate)
2 CO2 are released (1 per pyruvate)
The Citric
Aerobic Acid Cycle
cells use a
metabolic
wheel – the
citric acid
cycle – to
generate
energy by
acetyl CoA
oxidation
The citric acid cycle
acetyl CoA

citrate
oxaloacetate

malate isocitrate

fumarate
-ketoglutarate

succinate succinyl
CoA
Names: Hans Adolf Krebs.
Biochemist; born in Germany.
The Citric Acid Worked in Britain. His
discovery in 1937 of the
Cycle ‘Krebs cycle’ of chemical
reactions was critical to the
Tricarboxylic understanding of cell
Acid Cycle metabolism and earned him
the 1953 Nobel Prize for
Krebs Cycle Physiology or Medicine.

In
eukaryotes
the reactions
of the citric
acid cycle
take place
inside
mitochondria
Produces more ATP and releases more
electrons
–Electrons picked up by NAD + and FAD
- Organic carrier molecules
Occurs inside mitochondria
–Mitochondrial Matrix
Citric Acid (Krebs) Cycle
1. Citrate Synthase

• Citrate formed from acetyl CoA and oxaloacetate


• Only cycle reaction with C-C bond formation
• Addition of C2 unit (acetyl) to the keto double bond
of C4 acid, oxaloacetate, to produce C6 compound,
citrate

citrate synthase
2. Aconitase

• Elimination of H2O from citrate to form C=C bond


of cis-aconitate
• Stereospecific addition of H2O to cis-aconitate to
form isocitrate

aconitase aconitase
3. Isocitrate Dehydrogenase

• Oxidative decarboxylation of isocitrate to


a-ketoglutarate
• One of four oxidation-reduction reactions of the cycle
• Hydride ion from the C-2 of isocitrate is transferred to
NAD+ to form NADH
• Oxalosuccinate is decarboxylated to a-ketoglutarate

isocitrate dehydrogenase isocitrate dehydrogenase


4. The -Ketoglutarate Dehydrogenase Complex

-ketoglutarate
dehydrogenase
5. Succinyl-CoA Synthetase

+ HS
Succinyl- -
CoA
Synthetase

GTP + ADP GDP + ATP


6. The Succinate Dehydrogenase Complex

Succinate
Dehydrogenase
7. Fumarase

• Stereospecific trans addition of water to the


double bond of fumarate to form malate

Fumarase
8. Malate Dehydrogenase

• Malate is oxidized to form oxaloacetate.

Malate
Dehydrogenase
 2 carbon atoms
enter the cycle in
the form of acetyl
CoA.
 2 carbon atoms
leave the cycle in
the form of CO2.
 4 pairs of
hydrogen atoms
leave the cycle in 4
oxidation reactions
(3 molecules of
NAD+ & 1 molecule
of FAD are
reduced).
 1 molecule of GTP,
is formed.
 2 molecules of
water are consumed.
• The 8 steps:
1) Production of citrate
2) Isomerization
3) Oxidation
4) Oxidation
5) Conversion
6) Oxidation
7) Hydration
8) Oxidation
Electron Transport Chain
• What is the ETC???
– A series of molecules along which electrons
are transferred, releasing energy

– Occurs in the mitochondria—


wall of mitochondria

– Aerobic process
• Oxygen is involved
– Acts as the electron acceptor
Electron Transport Chain

• As the electrons are passed between


carrier proteins, energy is released
– ATP is created

• Electrons are given up by the carrier


molecules
– NADH and FADH2 ------- NAD + and FAD
Complex I – NADH dehydrogenase complex
Complex II – Succinate dehydrogenase complex
Complex III – Cytochrome bc1 complex
Complex IV – Cytochrome oxidase complex
SummarySummary

Mitochondrion

Electrons carried in NADH

Electrons carried
Pyruvic acid
in NADH and
FADH2
Glucose Krebs Electron
Glycolysis Transport
Cycle
Chain

Mitochondrion
Cytoplasm
Cellular Respiration

General Formula
C6H12O6 + 6 O2 6 CO2 + 6 H2O
Learning Outcome
Students should be able to :
• explain the carbohydrate function and
structure
• analyse the carbohydrate metabolism for
cellular respiration
• differentiate aerobic and anaerobic
metabolism to generate energy
THANK YOU!!!

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